Valorization of Phenolic and Carotenoid Compounds of Sechium edule (Jacq. Swartz) Leaves: Comparison between Conventional,Ultrasound- and Microwave-Assisted Extraction Approaches

Chayote leaves are known for culinary and traditional medicine applications. This work intended to recover carotenoids and phenolic compounds from chayote leaves using the ultrasound-assisted extraction (UAE). A Box–Behnken design was employed to investigate the impact of extraction time, temperature, and ultrasonic power on the recovery of total carotenoids, total phenolic compounds, and antioxidant activities. For comparative purposes, chayote leaf extracts were prepared by maceration (ME) and microwave-assisted extraction (MAE), using the same time and temperature conditions optimized by UAE. Extraction at 50 °C and 170 Watts for 30 min provided the optimal UAE conditions. UAE showed better extraction efficacy than ME and MAE. The HPLC analysis of the extracts showed that the xanthophyll class was the main class of carotenoids, which constituted 42–85% of the total carotenoid content, followed by β-carotene and tocopherol. Moreover, 26 compounds, classified as phenolic acids, flavonols, flavonoids and other polar compounds, were identified in the chayote leaf extracts. Flavonols accounted for 55% of the total compounds quantified (the major compound was myricetin) and phenolic acids represented around 35%, mostly represented by ferulic acid, chlorogenic acid and (+)-catechin. This study revealed the potential of UAE as an effective green extraction technique to recover bioactive compounds from chayote leaves, for food, and for pharmaceutical and cosmetic applications.     

Untersuchung von Butter, Margarine, Tran und anderen Fetten

Ohne Zusammenfassung     

Adsorption and recovery issues of recombinant monoclonal antibodies in reversed‐phase liquid chromatography†

The poor recovery of large biomolecules is a well‐known issue in reversed‐phase liquid chromatography. Several papers have reported this problem, but the reasons behind this behavior are not yet fully understood. In the present study, state‐of‐the‐art reversed‐phase wide‐pore stationary phases were used to evaluate the adsorption of therapeutic monoclonal antibodies. These biomolecules possess molar mass of approximately 150 000 g/mol and isoelectric points between 6.6 and 9.3. Two types of stationary phases were tested, the Phenomenex Aeris Widepore (silica based), with 3.6 μm superficially porous particles, and the Waters Acquity BEH300 (ethylene‐bridged hybrid), with 1.7 μm fully porous particles. A systematic investigation was carried out using 11 immunoglobulin G1, G2, and G4 antibodies, namely, panitumumab, natalizumab, cetuximab, bevacizumab, trastuzumab, rituximab, palivizumab, belimumab, adalimumab, denosumab, and ofatumumab. All are approved by the Food and Drug Administration and the European Medicines Agency in various therapeutic indications and are considered as reference antibodies. Several test proteins, such as human serum albumin, transferrin, apoferritin, ovalbumin, and others, possessing a molar mass between 42 000 and 443 000 g/mol were also evaluated to draw reliable conclusions. The purpose of this study was to find a correlation between the adsorption of monoclonal antibodies and their physicochemical properties. Therefore, the impact of isoelectric point, molar mass, protein glycosylation, and hydrophobicity was investigated. The adsorption of intact antibodies on the stationary phase was significantly higher than that of proteins of similar size, isoelectric point, or hydrophobicity. The present study also demonstrates the unique behavior of monoclonal antibodies, contributing some unwanted and unpredictable strong secondary interactions.     

Controlling the retention in capillary LC with solvents, temperature, and electric fields

Once a suitable stationary phase and column dimensions have been selected, the retention in liquid chromatography (LC) is traditionally adjusted by controlling the mobile phase composition. Solvent gradients enable achievement of good separation selectivity while decreasing the separation time as compared to isocratic elution. Capillary columns allow use of other programming parameters, i.e. temperature and applied electric fields, in addition to solvent gradient elution. This paper presents a review of programmed separation techniques in miniaturized LC, including retention modeling and method transfer from the conventional to micro- and capillary scales. The impact of miniaturized instrumentation on retention and the limitations of capillary LC are discussed. Special attention is focused on the gradient dwell volume effects, which are more important in micro-LC techniques than in conventional analytical LC and may cause significant increase in the time of analysis, unless special instrumentation and (or) pre-column flow-splitting is used. The influence of temperature upon retention is also discussed, and applications where the temperature has been actively used for retention control in capillary LC are included together with the instrumentation utilized. Finally the possibilities of additional selectivity control by applying an electric field over a packed capillary LC column are discussed.     

Noncovalent complexes between dimethyl ether and formic acid--an ab initio and matrix isolation study.

The complexes formed by noncovalent interactions between formic acid and dimethyl ether are investigated by ab initio methods and characterized by matrix isolation spectroscopy. Six complexes with binding energies between -2.26 and -7.97 kcal mol(-1) (MP2/cc-pVTZ+zero point vibrational energy+basis set superposition erros) are identified. The two strongest bound complexes are, within a range of 0.3 kcal mol(-1), isoenergetic. The binding in these six dimers can be described in terms of OH...O, C=O...H, C-O...H and CH...O interactions. Matrix isolation spectroscopy allowed to characterize the two strongest bound complexes by their infrared spectra.     

Efficient production of enol ether radical cations by heterolytic cleavage of beta-mesylate radicals

[reaction: see text] alpha-Methoxy-beta-mesyloxy radicals were produced in laser flash photolysis reactions, and yields of enol ether radical cations formed by heterolytic fragmentation of the mesylate group were determined. The mesylate heterolysis reaction is faster than heterolyses of phosphate and bromide groups in analogous radicals and highly efficient in medium-polarity solvents.     

Effect of the addition of a nonaqueous polar solvent (glycerol) on enzymatic catalysis in reverse micelles. Hydrolysis of 2-naphthyl acetate by alpha-chymotrypsin

The kinetics of hydrolysis of 2-naphthyl acetate (2-NA) catalyzed by alpha-chymotrypsin (alpha-CT), in reverse micellar solutions formed by glycerol (GY)-water (38% v/v) mixture/sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/n-heptane has been determined by spectroscopic measurements. To compare the efficiency of this reaction with that observed in micelles with water in the core, as well as in the corresponding homogeneous media, the reaction was also studied in water/AOT/n-heptane reverse micellar solutions and in both homogeneous media (water and GY-water, 38% v/v mixture). In every media, alpha-CT was characterized by the absorption and emission spectra, the fluorescence lifetimes, and the fluorescence anisotropy of its tryptophan residues. The effect of AOT concentration on the kinetic parameters obtained in the micellar systems was determined, at a constant molar ratio of the inner polar solvent and surfactant. Moreover, the data obtained allowed the evaluation of the 2-NA partition constant between the organic and the micellar pseudophase. It is shown that the addition of GY to the micelle interior results in an increase in the catalytic properties of alpha-CT. The fluorescence anisotropy studies in the different media show that the addition of GY increases the viscosity as compared with the aqueous systems. It seems that the GY addition to the reverse micellar aggregates results in a decrease of the conformational mobility of alpha-CT, which leads to an increase of the enzyme stability and activity.     

The synthesis and properties of new carbohydrate‐modified mesoionic thiazolo[3,2‐α]pyrimidine‐5,7‐dione acyclonucleosides

The synthesis of the first examples of Class II mesoionic thiazolopyrimidine acyclonucleosides (MTA) incorporating the 2,3‐dihydroxypropyl moiety as the sugar simulator is described. First, 2‐bromothiazole was reacted with excess 1‐amino‐2,3‐propanediol acetonide via an aromatic nucleophilic substitution reaction to yield 1‐(2‐thiazolylamino)‐2,3‐propanediol acetonide. This acetonide intermediate was condensed at 160° with substituted bis(2,4,6‐trichlorophenyl) malonic esters to form a series of protected acyclonucleosides termed anhydro‐(8‐((2,2‐dimethyl‐1,3‐dioxolan‐4‐yl)methyl)‐5‐hydroxy‐7‐oxothiazolo[3,2‐a]pyrimi‐dinium hydroxides) which differ in their 6‐position substituent. Deprotection of these acyclonucleosides using p‐toluenesulfonic acid catalyst in methanol at 65° yielded the desired Class II MTA, anhydro‐(8‐(2,3‐dihydroxypropyl)‐5‐hydroxy‐7‐oxothiazolo[3,2‐a]pyrimidinium hydroxides).